Organosilicon polyboranes



United. States Patent 1 2,902,505.. ORGANQSIHGON- BOLYBORANES Dietmar Seyferth, Midland, Mich., assignor to Dow Got,- g Corporatiom, Midland, Mieh., a corporation of Michigan No-Drawing fipplicatibn Marcli 5, 1956" SeriahNoa569g-223 QJCIaiI nS. (CL. fill-44.812)" This invention relates to novel organosilicon compounds containing two:.or: more: boron: atoms per molecule; ltti sfihesobject. ofitliis. invention to provide novel organosiliconcomponndstof' boron which are soluble in .organopolysiloxane...fluidsandtwhich are useful'as oxygen Scavengers for such flilids. Another object is to provide new compositionsof. matter. which areuseful in stabilizing lubricants, hydraulic.fluids, dielectric fluids and fluids forjelectronic devices.

This. invention relates. to compounds of the formula p I I A (C i0 -]m(B a); inwhich x is an integer from' 0 to 1', R is a monovalent hydrocarbon radical, R is of the group hydrogen and alkyl radicals, mand m are bothintegers of at least 1.

The compositions within the scope of the above generic formula.'comprise two basic species; The first species includes. disil'oxanediboranes ofithe general formula R R2 RiIL A I R IB(CH),.SiOSi(CH),,IBRg These materialsarebest prepared'by; a Barbier reaction involving addition of a mixture of a hydrocarbon. halide,

a trihaloborane or a trial koxy borane and" a disiloxane of the formula R R R: R v .XICHMSlOSKCHMXQ (Kid-halogen); iirthemolar ratio ofq, 1: andnS' re spectively, to'magrfesium in-etherz This reaction will Proceeti-in 'the conventionalmanner for carrying out -Barbier* reactions.'- After-reaction is complete-i the magnesiumsalts are filtered oflz' 'and the product recovered from the ether solution.

These-disiloxanediboranecan'be copolymerized with "conventionaldiorganosiloxanes by conventional alkaline or acid equilibration procedures to give cop'olymers of The .second. .basicspecies-of this invention. includes polymeric siloxane boranes. of the: unit formula This type of. 'compound is also best 'prepared by the above described Barbier reaction-except that the reactants are employed in the molar ratio of 1 mol hydrocarbon l inol ofit'r'ihalo or triallioxy borane and .5 moljof These polymeric siloxane boranes can be interacted with diorganosiloxanes of the unit formula R SiO to give copolymers having the molecular structure 5 or any alkyl. radical suchas. methyl, ethyl or octadecyl.

in. which a: and It can: be varied to give any desired proportion of boron; containing units.. Thus a1 and b range from .001: to 9.9.99 9. The secondspecies can also be interacted with triorganosiloxanes to give polymers of the formula nin RR"' R;

R,s1Q[Si(0H)..B (0H),.Sl01mSlR; v p in which m has a value.of at least 2. These latter two types of copolymers are al'so'prepared by conventional alkaline interaction commonly used for preparing siloxane copolymers:

For the purpose of this invention the R groups 'on the boron and on the silicon can be any monovalent hydrocarbon radical'such as alkyl radicals such as methyl, ethyl, butyl and octadecyl; alkenyl radicals such as vinyl, allyl and hexenyl; cyloaliphatic radicals such as cyclohexyk cyclopentyl and cycyoliexenyl," aralkyl radicals such as benzylian'd aromaticihydrocarbon radicals such as-ph'enyl, xenyl, tolyl, naphthyl: and x'ylyl.v It should be:unde1 stood that in any particular molecule all the R groups can be the same or there can be any combination of different: R. groups: attached to the boron and silicon atoms. a

For the purpose of this invention R can be hydrogen With respect to the R groups it should be understood that where n is greater than. 1,.some of the R"can be hydrogen and some alkyl. Thus, specific examples of i hRl l h u u s are H5).

Me Me Me (CHgCHCHz), (CHOH) and (CH CH cHgcH The following examplesare illustrative only -and"should not be construed as limitingtheinvention which is properly'delineatedfinithe appendedclaims. In the formulas 'belownthe. hydrocarbonzradicalsare designated by the first 'twolettersain. their names such asMe'f'or methyl lh fomzz' plrenyl; Vi for: vinyl, etc.

Example 1 24.32 g. of magnesium-imZ'SO-ml. of ether was activated with a few mol of butyl magnesium bromide and a mixture of g. of bis-chloromethyltetramethyldisiloxane, 46 g. of butyli bromide and 35 g. of trimethoxy .borane was run into the activated.magnesium-ether mixture. Anexothermic reaction took" place. Afterthe reaction. subsided the.m'ixture. was refluxedfor 3 hours. Themagnesfim salts were then hydrolyzed withsaturated ammonium chloride solution and'the' organic'layer'decanted and dried over anhydrous sodium sulfate. The ether was then removed'by distillation and the residue was shown by analysis to be essentially a polymer of the unit formula Bu' MBaMez (BCHgSiOSiCHz):

This material was in the form of a yellowish oil.

A 5 percent solution of this oil in 30 g. of a 200 cs. trimethyl. endeblocked. dimethylpolysiloxane fluid abs0rhed;82.3 ccaof oxygen under standard conditions of temperature and: pressures Example 2 l mixture of .22 mol of bis-chloromethyltetramethylworked up in the manner of Example 1. The product was a yellow oil having the formula MezMez 3111B CHgSlOSlCHgB Bu,

3. A composition of matter having the formula MezMez BUzBCHgSlOSiCHgBBIh 4. A copolymeric composition of matter having the A five percent solution of this oil in 30 g. of the 5 general formula selected from the group consisting of siloxane in Example 1, absorbed 61 cc. of oxygen under standard conditions of temperature and pressure.

Example 3 When 1 mol of BF -Et o, 2 mols of vinyl magnesium bromide and .5 mol of the compound Me Ph B11 OlOHgCHCHgSiOSiCHgCl Me V1 is reacted in the manner of Example 2, the fluid compound Me Ph Bu VinB CHzC HG H SiOSiCHgB Vi,

Me V1 is obtained.

Example 4 When 1 mol of B(OMe) 1 mol of phenyl magnesium bromide and /2 mol of the compound Me Me Elli Phq Me Me ClCHOHSiOSi--CHCHCI are reacted in accordance with the procedure of Example 1, the fluid polymeric compound Ph Me Me Et PhzMe Me (B-H-(JH-si-0-s1oH-0H)- is obtained.

Example 5 When 1804 g. (8 mols) of the siloxane borane of Example 1 is interacted With 1 mol of hexamethyldisiloxane in the presence of .1 g. of the salt Me SiOK at 90 C. a fluid copolymer of the average formula Meg Bu Me Me Si0 (SiCHzB CH SlO) 381MB;

is obtained.

Example 6 When 22.8 g. (.1 mol) of the fluid borane siloxane of Example 1 is interacted with 122.4 g. (.9 mol) of phenylmethylsiloxane at 150 C. in the presence of 2 g. of Me SiOK, a fluid copolymer of the average composition M82 Bu Me, P11 (SiCH2BCH2SiO).1(SlO).s

is obtained.

Example 7 When a mixture of 1 mol of the siloxane borane of Example 2 and 1 mol of (MeViSiO) is heated at 100 C. in the presence of .1 g. of Me SiOK, a fluid copolymer of the average formula is obtained.

That which is claimed is: 1. A composition of matter having formula the general Bu Mei Me: -n CHgSlO SiOHr-) integer of at least 2.

5. A copolymeric composition of the general formula R R; R, R R' Rm(0H),.sio(si0),,si(cH),.BR, in which R is a monovalent hydrocarbon radical, R is of the group consisting of hydrogen and alkyl radicals and n and y are both integers of at least 1.

6. A copolymeric composition of the general formula R2 R R R R3 R1 [Si(CH),.B(CH),.S1OL1(Sl0)a in which R is a monovalent hydrocarbon radical, R is of the group consisting of hydrogen and alkyl radicals, n is an integer of at least 1 and a and b both vary from .001 to 99.999.

7. A copolymeric composition of matter having the general formula R R R R R: R,s10[s1(oH)..B(0H),.si0]..s1R, in which R is a monovalent hydrocarbon radical, R is of the group consisting of hydrogen and alkyl radicals, n is an integer of at least 1 and m is an integer of at least 2.

8. A method of preparing copolymeric compositions which comprises interacting (1) a compound of the general formula R R R1 RIB [B(CH),,SiOSl(OH),.-=

R is a monovalent hydrocarbon radical, R is selected from the group consisting of hydrogen and alkyl radicals and n and m are both integers of at least 1, with (2) a siloxane in which the siloxane units are of the group consisting of R SiO and R SiO. units in which R is a monovalent hydrocarbon radical, whereby a copolymer of (1) and (2) is formed.

9. A method of preparing copolymeric compositions which comprises interacting (1) a compound of the general formula monovalent hydrocarbon radical, whereby a copolymer of (1) and (2) is formed.

References Cited in the file of this patent UNITED STATES PATENTS Patnode Jan. 27, 1948 Upson Aug. 8, 1950 UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,902,505 September 1, 1959 Dietmar Seyferth It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, lines 34 and 35, the formula should read as shown below instead of as in the patent:

- a lau h) n%) S i :E[) BRa column 2, line 17 for cycyohexenyl read cyclohexenyl-; column 3, lines 37 and 38, the formula should read as shown below instead of as in the patent:

Me; Bu Men MezSiO (SiCHzB CHzSiO) sSiMea column 4, lines 8 and 9, the formula should read as shown below instead of as in the patent:

R2 R R R2 R2 [Si(CH)nB(OH),.Sio](SiO)a column 4, line 46, before R insert -in which.

Signed and sealed this 26th day of April 1960.

Attest: KARL H. AXLINE, ROBER'I C. WATSON, Attestzng Oyfioer. Oomam'ssz'oner of Patents.

UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,902,505 September 1, 1959 Dietmar Seyferth It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, lines 34 and 35, the formula should read as shown below instead of as in the patent:

R. R5 R2 R RRB(Cl'I) SlOSl(CH)nBRH column 2, line 17 for cycyohexenyl read -oyelohexeny1; column 3, lines 37 and 38, the formula should read as shown below instead of as in the patent:

Meg Bu Mei MeaSiO (SiCH2B O HgSiO) sSi'Mez column 4, lines 8 and 9, the formula should read as shown below instead of as in the patent:

R; R R R R1 R2 [Si(GH),.B(CH),.Si0]a(SiO)t column 4, line 46, before R insert -in whioh-.

Signed and sealed this 26th day of April 1960.

[SEAL] Attest:

KARL H. AXLINE, ROBERT C. WATSON, Attestz'ng Oficer. Oommz'ssz'oner of Patents. 

1. A COMPOSITION OF MATTER HAVING THE GENERAL FORMULA 